In Situ Chemical Oxidation of RDX‐Contaminated Groundwater with Permanganate at the Nebraska Ordnance Plant

Albano, Jeffrey; Comfort, Steve D.; Zlotnik, Vitaly A.; Halihan, Todd; Burbach, Mark E.; Chokejaroenrat, Chanat; Onanong, Sathaporn; Clayton, Wilson S.

doi:10.1111/j.1745-6592.2010.01295.x

Cited by 16 publications

(22 citation statements)

References 24 publications

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“…S6B). Although the magnitude of 373 NO 3 -generated was similar to what we observed when MnCO 3 was used as a 374 quenching agent (Fig. S6A, S6B (Fig.…”

Section: Si-3 Experimental Controls 228supporting

confidence: 75%

“…To accurately quantify RDX and degradation product concentrations during oxidation by MnO 4 − , samples were quenched to prevent further RDX transformation. To avoid interferences during RDX and degradate analyses, three different quenching agents were tested (MnSO 4 , MnCO 3 , and H 2 O 2 ). The choice of quenching agent was found to influence pH and product distribution (see Supporting Information, SI-4).…”

Section: Methodsmentioning

confidence: 99%

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Transformation of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Permanganate

Chokejaroenrat

Comfort

Harris

et al. 2011

Environ. Sci. Technol.

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IntroductionHexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common groundwater contaminant at numerous military sites where munitions were either formulated, manufactured, or used in military exercises. Permanganate (MnO 4 − ) is an oxidant commonly used with in situ chemical oxidation (ISCO) and has been widely accepted for treating chlorinated ethenes. Past research has shown that MnO 4 − preferentially attacks compounds with carbon−carbon double bonds, aldehyde groups, or hydroxyl groups and is attracted to the electron-rich region of chlorinated alkenes.(1) Although RDX possesses none of these characteristics, laboratory studies performed by Adam et al.(2) showed that MnO 4 − could effectively transform and mineralize RDX (i.e., ~87% recovered as 14 CO 2 ). Moreover, a pilotscale demonstration at the Nebraska Ordnance Plant further supported MnO 4 − as a possible in situ treatment for RDX-contaminated groundwater.(3) Despite demonstrating efficacy in removing RDX from tainted waters, the reaction rates and mechanisms by which MnO 4 − transforms RDX (and other explosives) have not been thoroughly studied.(4) While a carbon mass balance of the RDX−MnO 4 − reaction has been observed,(2) a similar nitrogen mass balance for this reaction has not been reported.One analytical challenge to identifying degradation products in a MnO 4 − matrix is that the solution is highly colored (i.e., purple), so colorimetric and UV detection techniques are not possible unless samples are quenched to remove MnO 4 − before analysis. However, the choice of quenching agent may influence pH or product distribution and further complicates understanding the RDX−MnO 4 − reaction mechanism.The transformation of RDX by various treatments has revealed several possible reaction pathways. These include direct ring cleavage, nitro-group reduction, concerted decomposition, and N-denitration.(5-12) While intermediates produced by some of these pathways are fleeting and difficult to mea- AbstractThe chemical oxidant permanganate (MnO 4 − ) has been shown to effectively transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at both the laboratory and field scales. We treated RDX with MnO 4 − with the objective of quantifying the effects of pH and temperature on destruction kinetics and determining reaction rates. A nitrogen mass balance and the distribution of reaction products were used to provide insight into reaction mechanisms. Kinetic experiments (at pH ~7, 25 °C) verified that RDX−MnO 4 − reaction was first-order with respect to MnO 4 − and initial RDX concentration (second-order rate: 4.2 × 10 −5 M −1 s −1 ). Batch experiments showed that choice of quenching agents (MnSO 4 , MnCO 3 , and H 2 O 2 ) influenced sample pH and product distribution. When MnCO 3 was used as a quenching agent, the pH of the RDX−MnO 4 − solution was relatively unchanged and N 2 O and NO 3 − constituted 94% of the N-containing products after 80% of the RDX was transformed. On the basis of the preponderance of N 2 O produced under neutral pH (molar ratio N 2 O/...

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“…S6B). Although the magnitude of 373 NO 3 -generated was similar to what we observed when MnCO 3 was used as a 374 quenching agent (Fig. S6A, S6B (Fig.…”

Section: Si-3 Experimental Controls 228supporting

confidence: 75%

Section: Methodsmentioning

confidence: 99%

Transformation of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Permanganate

Chokejaroenrat

Comfort

Harris

et al. 2011

Environ. Sci. Technol.

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“…Electrical resistivity imaging (ERI) was used to identify the location of the permanganate after injection. Despite problems in getting the permanganate evenly distributed throughout the well screen, pilotscale results showed that RDX concentrations decreased in wells closest to the injection wells by 70-80 % [405].…”

Section: Permanganatementioning

confidence: 99%

“…Regardless of the pathway, it is clear that permanganate is capable of transforming and mineralizing RDX [382,404]. To scale up these observations, Albano [405] recently conducted a pilotscale test using permanganate on a test section of RDX-contaminated groundwater at the Nebraska Ordnance Plant. The pilot-scale ISCO was performed by using an extraction/injection well configuration to create a curtain of permanganate between two injection wells.…”

Section: Permanganatementioning

confidence: 99%

Soils contaminated with explosives: Environmental fate and evaluation of state-of-the-art remediation processes (IUPAC Technical Report)

Kalderis

Juhasz

Boopathy

et al. 2011

Pure and Applied Chemistry

155

143

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An explosion occurs when a large amount of energy is suddenly released. This energy may come from an over-pressurized steam boiler, from the products of a chemical reaction involving explosive materials, or from a nuclear reaction that is uncontrolled. In order for an explosion to occur, there must be a local accumulation of energy at the site of the explosion, which is suddenly released. This release of energy can be dissipated as blast waves, propulsion of debris, or by the emission of thermal and ionizing radiation.Modern explosives or energetic materials are nitrogen-containing organic compounds with the potential for self-oxidation to small gaseous molecules (N 2 , H 2 O, and CO 2 ). Explosives are classified as primary or secondary based on their susceptibility of initiation. Primary explosives are highly susceptible to initiation and are often used to ignite secondary explosives, such as TNT (2,4,6-trinitrotoluene), RDX (1,3,5-trinitroperhydro-1,3,5-triazine), HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), and tetryl (N-methyl-N-2,4,6-tetranitroaniline).

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“…Past work by Adam et al (2004) showed that permanganate could effectively mineralize RDX in the presence of aquifer solids. Using sediments and groundwater from the NOP, Albano (2009) performed treatability experiments and confirmed that site conditions at NOP were conducive to using permanganate as an ISCO treatment. The first objective of this study was to determine the efficacy of permanganate to transform RDX at the field scale by performing a pilot‐scale in situ chemical oxidation (ISCO) demonstration (Albano et al 2010).…”

Section: Introductionmentioning

confidence: 85%

Electrical Resistivity Imaging of a Permanganate Injection During In Situ Treatment of RDX‐Contaminated Groundwater

Halihan¹,

Albano²,

Comfort³

et al. 2011

Groundwater Monitoring Rem

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Groundwater beneath the former Nebraska Ordnance Plant (NOP) is contaminated with the explosive hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and trichloroethene (TCE). Previous treatability experiments confirmed that permanganate could mineralize RDX in NOP aquifer material. The objective of this study was to determine the efficacy of permanganate to transform RDX in the field by monitoring a pilot‐scale in situ chemical oxidation (ISCO) demonstration. In this demonstration, electrical resistivity imaging (ERI) was used to create two‐dimensional (2‐D) images of the test site prior to, during, and after injecting sodium permanganate. The ISCO was performed by using an extraction‐injection well configuration to create a curtain of permanganate. Monitoring wells were positioned downgradient of the injection zone with the intent of capturing the permanganate‐RDX plume. Differencing between ERI taken preinjection and postinjection determined the initial distribution of the injected permanganate. ERI also quantitatively corroborated the hydraulic conductivity distribution across the site. Groundwater samples from 12 downgradient wells and 8 direct‐push profiles did not provide enough data to quantify the distribution and flow of the injected permanganate. ERI, however, showed that the permanganate injection flowed against the regional groundwater gradient and migrated below monitoring well screens. ERI combined with monitoring well samples helped explain the permanganate dynamics in downgradient wells and support the use of ERI as a means of monitoring ISCO injections.

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In Situ Chemical Oxidation of RDX‐Contaminated Groundwater with Permanganate at the Nebraska Ordnance Plant

Cited by 16 publications

References 24 publications

Transformation of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Permanganate

Transformation of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by Permanganate

Soils contaminated with explosives: Environmental fate and evaluation of state-of-the-art remediation processes (IUPAC Technical Report)

Electrical Resistivity Imaging of a Permanganate Injection During In Situ Treatment of RDX‐Contaminated Groundwater

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